US3725382A - Difluoropyrimidylamino-group-containing metallized water-soluble reactive formazane dyes - Google Patents

Abstract

Metal complexes of reactive water-soluble formazane dyes which contain 2, 3 or 4 sulfonic acid groups and one difluoropyrimidylamino group yield dyeings which have good fastness to light, washing, milling and perspiration.

Description

Q ilmted States Patent 1 1 Grandjean [4 1 Apr. 3, 1973 [54] DIFLUOROPYRIMIDYLAMINO- [56] References Cited GROUP-CONTAiNING METALLIZED UNITED STATES PATENTS EACTIVE 3,041,328 6/1962 Kraus et a1 ..260/ 146 D 3,068,219 12/1962 Beffa et a]. 260/146 D [75] Inventor: Philippe Grandjean, Basel, Switzer- 3,244,690 1966 60/146 D land 3,202,649 8/1965 Steinemann.... ..260/146 D 3,202,650 8/1965 Steinemann ..260/146 D [7 3] Assignee: Sandoz Ltd., Basel, Switzerland FOREIGN PATENTS OR APPLICATIONS [22] Filed: Mar. 26, 1970 1,330,585 5/1963 France ..260/153 [21] App1.No.: 23,024

Primary Examiner-Floyd D. Higel [30] Foreign A fi ti p i Data Attorney-Gera1d D. Sharkin, Thomas C. Doyle,

V 7 l Robert S. Honor, Walter F. Jewell; Thomas 0. Mc- Mar. 26, 1969 Sw1tzerland ..4656/69 Govern Richard Vila and Frederick w inf ldt Apr. 1, 1969 Switzerland ..4927/69 1 [57] ABSTRACT [52] US. Cl. ..260/146 D, 8/10, 8/42 R,

260/149, 260/154 260/193 Metal complexes of react1ve water-so1uble formazane [51] Int Cl. "mC09b 45/18 C09b62l24 Dop H38 dyes which contain 2, 3 or 4 sulfonic acid groups and 58 Field of Search ..260/146 D, 146 T, 153, 154 diflwmPYimidylamino Yield dyeings which have good 'fastness to light, washing, milling and perspiration.

5 Claims, No Drawings DIFLUOROPYRIMIDYLAMINO-GROUP- CONTAINING METALLIZED WATER-SOLUBLE REACTIVE FORMAZANE DYES This invention relates to a process for the production of reactive, water-soluble metal complex compounds which, in the metal-free state, have the formula where X stands for a hydrogen, chlorine, bromine or fluorine atom or for a lower alkyl group which may be substituted,

Y for hydrogen or a group Z for a lower alkyl group which may be substituted or an amino group which may be monosubstituted,

n for 2, 3 or 4,

p for l, 2 or 3,

where the sum ofn and p is 3, 4 or 5,

R, and R each stands for a benzene or naphthalene radical which bears the OH group in ortho position to -N= or -Nl-l and may be substituted,

R for a hydrogen atom or for an aliphatic radical which may be substituted,

R for an aliphatic or cycloaliphatic, radical which may be substituted or for a benzene or naphthalene radical which may be substituted,

or R and R jointly with the adjacent N atom, form a heterocyclic ring. Copper complex compounds which, in the copper-free state, conform to the general formula (l), where X stands for chlorine,

n for 2 or 3,

p for 1 and R and R for benzene or toluene radicals which bear the OH group in ortho position to 'N= or NH-, are dyes of notably good quality.

The process of this invention consists of reacting l mole of metal complex ofa compound of the formula with 1 mole ofa polyfluoropyrim'idine of the formula (III) The metal complexes of the compounds of formula (ll) which are used as starting materials in the process can be produced by the methods described in French Pat. 1,330,585 and British Pat. 1,022,043.

The lower, optionally substituted, alkyl or alkoxy groups may be, e.g., alkyl or alkoxy groups having one to five carbon atoms. They may be straight or branched and may bear substituents, such as hydroxyl or lower alkoxy groups (-OCH ,OC H

If the radical Z represents a monosubstituted amino group, the substituent at the amino group is a lower alkyl radical which may bear substituents, such 1 as hydroxyl and lower alkoxy groups, or the phenyl radical which may bear carboxylic or sulfonic acid groups. Suitable groups of formula SO -Z are, for example,

, lower alkylsulfonyl groups (SO CH -SO C H SO CH(CH and sulfonamide groups which may be monosubstituted, such as SO NH -SO NHCH SO NHC H OCH SO NHC H och SO NHC H The radicals R and R and likewise the radical R if it is aromatic, may bear substituents, such as lower alkyl groups (methyl, ethyl), lower alkoxy groups (methoxy, ethoxy), halogen atoms (chlorine, bromine, fluorine), the nitro group, the carboxyl group and acylamino groups, such as lower alkyl carbonylamino, lower alkoxy carbonylamino, aryl carbonylamino groups (acetylamino, propionylamino, butyrylamino, methoxycarbonylamino, ethoxycarbonylamino, benzoylamino).

If the radical R represents optionally substituted alkyl or alkylene radicals, it may contain one to 10 carbon atoms, may be straight or branched and may bear substitutents, such as hydroxy, lower alkoxy, carboxy or phenyl groups.

If the radical R represents optionally substituted alkyl, alkenyl or cycloalkyl radicals with five to l2 members in the carbocyclic ring, it may bear substituents, such as hydroxy, lower alkoxy, carboxy, cyclohexyl, phenyl or sulfonic acid groups or 5-membered heterocyclic radicals with O or N- hetero atoms. The preferred cycloaliphatic radicals are the cyclohexyl radical and its derivatives having lower alkyl groups (methyl, ethyl).

If the radical R represents optionally substituted phenyl or naphthyl radicals, it may bear substituents, such as hydroxy, lower alkoxy, carboxy, sulfonic acid, amidosulfonyl, anilidosulfonyl, trifluoromethyl groups or halogen.

If the radicals R and R jointly with the adjacent N atom, form a heterocyclic ring, the latter is a five, six or seven-member ring which may be substituted by lower alkyl or carboxy groups and which contains one N or one N and one 0 hetero atom.

In the radical v, W a

denoted Y, examples of groupsoffoi'mula 7 Rs CON which are of special interest are methyl-, ethyl-, n"-

propyl-, isopropyl-, n-butyl-, isobutyl-, tert.butyl-, N- amyl-, isoamyl-, n-hexyl, n-hepty|-, n-octyland 2- ethylhexylamino groups; the dimethyl-, diethyl-, diisopropyl-, di-n-propyland di-n-butylamino groups; the allylamino group, the 2-hydroxyethyl-, 2-hydroxypropyl-, 3-hydr0xypropyl-, l-hydroxybutyl-2-, lhydroxy-2-methylpropyl-2-amino groups; the bis-(2- hydroxyethyl)-, bis-(2-hydroxypropyl)-amino groups; the N-methyl-N-2-hydroxyethyl-, N-ethyl-N-2-hydroxyethyland, N-n-propyl-N-2-hydroxyethylamino groups; the 2-methoxyethyl-, 2-ethoxyethyl-, 3- methoxypropyl-, 3-ethoxypropyl-, 3-isopropoxypropyl- 3-n-butoxypropyland, 4-methoxybutylamino groups; the bis-(2-ethoxyethyl)-amino, carboxymethylamino, N-methyl-N-carboxymethylamino, 2-carboxyethylamino, benzylamino, furfurylamino, N-methyl- N-benzylamino, cyclohexylamino, 4-methylcyclohexylamino, N-methylN-cyclohexylamino and, N-ethyl-N- cyclohexylamino groups; the phenylamino, 2-, 3- or 4- methylphenylamino, 2,4-, 2,5- or 2,6-dimethylphenylamino, 2,4,6-trimethylphenylamino, 2-, 3- or 4- chlorophenylamino-, 2- or 4-methoxyor -ethoxyphenylamino, 3- or 4-aminosulphonylphenylamino, 2- or 4- carboxyphenylamino and, 4-hydroxy-3-carboxyphenylamino groups; the N-methyl-, N-ethyl-, N-isopropyl-, N-n-propylor N-n-butyl-N-phenylamino, N-ethyl-N-4- methylphenylamino, N-methyl-N-2-carboxyphenylamino, N-2-hydroxyethyl-N-phenylamino and, N-2- hydroxyethyl-N-3-methylphenylamino groups; the morpholino, piperidino, pyrrolidino or hexamethylenimino groups; the l-naphthylamino and 2- naphthylamino groups.

The SO H groups, the SO Z groups when present and also the reactive radical may be bound to the radicals R, and R and to the radical R, when-the latter is aromatic. R and R may each contain not more than two of the aforenamed groups, but R, may bear 1, 2 or even 3 of such groups, for example 2 -SO H groups on R and 1 reactive radical on R2,

or 1 SO Z group on R,, 2 --SO H groups on R, and

1 reactive radical on R or 1 SO H group on R,, one SO ,Z group on R,,, l

SO H group and l reactive radical on R or 1 SO H group on R one -SO H group on R and l reactive radical on R or I -SO;,H group on each of R R and R and l reactive radical on R, or 1 reactive radical and l -SO H group on R and 2 SO H groups on R etc.

The reaction of the water-soluble dyes used as starting products with a compound of formula (III) is carried out preferably in aqueous medium. It may, however, be effected in an organic solvent or in a mixture of organic solvent and water, which can be of special advantage if the intermediate is poorly soluble or insoluble in water. 1

Suitable organic solvents for this purpose include alcohols, acetone, benzene, toluene and tertiary organic bases such as pyridine. The compound of formula (Ill) can be employed as it is in concentrated form or in solution in an organic solvent. Highly suitable organic solvents are acetone, benzene, chlorobenzene and toluene.

The reaction temperature is adjusted to the reactivity of the starting products and varies from 0 to 30 C, the preferred temperature range being l030 C.

The reaction is conducted in the neutral to weakly acid pH region of, e.g., pH seven to four. For neutralization of the equivalent of hydrogen fluoride which is formed, a buffer mixture, e.g., an acetateacetic acid mixture, is added to the solution at the commencement of the reaction, or an acid-binding agent is added in solid, pulverized form or in aqueous solution in the course of the reaction, suitable agents being sodium or potasium carbonate, sodium and potassium hydroxide, calcium and barium hydroxide. The addition of small amounts of a wetting or emulsifying agent accelerates the reaction rate.

The reaction is controlled so that only one fluorine atom of the compound of formula (III) reacts with an exchangeable hydrogen atom.

On completion of the condensation of coupling reaction the reaction solution or suspension may, if desired, be neutralized, after which the metal complex dye formed is precipitated with sodium or potassium chloride or acid, filtered off with suction, washed and dried under controlled condition.

As the new metal complex dues are highly reactive, it is advisable to add to them, either before or after drying, a buffer salt or a mixture of buffer salts which will maintain the pH value in the vicinity of the neutral point, e.g., in the pH region of five to seven, and so enhance their stability in storage as dry powders and in padding liquors or printing pastes prior to application.

The water-soluble dyes of this invention which bear a radical of the formula (IV) are suitable for the exhaustion dyeing, pad dyeing and printing of animal and vegetable fibers, regenerated cellulosic fibers, casein fibers, animalized cellulosic fibers, synthetic polyamide fibers, blends of the aforenamed fibers and leather. The dyeings, which, if necessary, may be submitted to an alkaline aftertreatment with heating followed by soaping have good fastness to light, washing, milling and perspiration. The dyes are applicable by continuous and semi-continuous methods, such as the pad-jig, pad-roll, pad-steam and thermofixation processes.

These new reactive dyes have good solubility in water, show good compatibility with salts and hard water and good reactivity with animal, vegetable and synthetic polyamide fibers. They reserve acetate, triacetate, polyester, poly'acrylonitrile, polyvinyl chloride, polyvinyl acetate and polyalkylene fibers. Owing to their good solubility in water, the unfixed proportion of the applied dye can be easily removed by washing from the dyed or printed goods.

The reactive dyes of this invention which bear only two sulphonic acid groups are well suitable for the exhaustion dyeing of cellulosic fibers and for the acid dyeing of wool, silk and synthetic polyamide fibers.

The dyeings and prints obtained with these dyes are of particularly high quality because the dyes form a stable chemical linkage with the fiber molecule, which normally imparts outstandingly food fastness to wet treatments. If the entire amount of applied dye does not react with the fiber, the unreacted amount can be cleared from the substrate by washing off and, if necessary, soaping, with heating to high temperatures as required. For this purpose synthetic detergents can be used, e.g., alkylaryl sulphonates (dodecylbenzene sulphonate), sodium lauryl, cetyl or oleylsulphate, sodium laurylpolyglycolether sulphates, monoalkyland dialkyl-phenylpolyglycol ethers, if desired in conjunction with sodium polyphosphate.

The dyed, padded or printed dyes are fixed on the fiber in the dyebath or in a fresh medium, if required after intermediate drying. If a fresh bath is used it is advisable to fix in the presence of a water-soluble salt, eg sodium sulphate, to prevent partial re-dissolving of the dye in the medium. Fixation of the dye radical on the fiber can be effected with heating, e.g., in steam or in dry heat as in the thermofixation process, or alternatively by storage at room temperature or at moderately high temperatures.

The optimum conditions of application for the dyes vary widely with the nature of the fiber. In exhaustion dyeing, padding and printing processes they are applied to animal and synthetic polyamide fibers preferably from an acid, neutral or weakly alkaline medium, e.g., in the presence of acetic, formic, sulphuric or oxalic acid, ammonium sulphate, sodium acetate, sodium bicarbonate, sodium or potassium carbonate, sodium metaphosphate, trimethylamine, pyridine, quinoline, etc. Dyeing can be carried out in an acetic acid to neutral bath in the presence of levelling agents, e.g., polyoxethylated fatty amines, or mixtures of these and alkylphenyl or alkylpolyglycolethers, and the bath adjusted to a neutral or weakly alkaline reaction at the end of dyeing by the addition of small amounts of an agent of alkaline reaction, e.g., ammonia, sodium carbonate or bicarbonate, or a compound which reacts alkaline on heating, e.g., hexamethylene tetramine. Subsequently the goods are well rinsed and if necessary acidified with acetic acid.

The exhaustion or pad dyeing and the printing of cellulosic fibers with the new dyes is best carried out in alkaline medium, e.g., in the presence of sodium carbonate or bicarbonate, caustic soda or caustic potash solution, calcium hydroxide, sodium metasilicate, sodium borate, water glass, trisodium phosphate, ammonia, trimethylamine, quaternary bases, e.g., tetra-alkylammonium compounds. To prevent reductive reactions in dyeing, padding or printing, it is often of advantage to add a mild oxidizing agent, such as sodium 1- nitrobenzene-3-sulphonate. Fixation on cellulosic as on other fibers can be accomplished with heating. However, given the use of moderately strong alkalis, such as sodium or potassium carbonate, the dyes can be applied in the cold, with fixation in a saturated sodium chloride or sulphate solution containing sodium carbonate, or by storage at room temperature. Fixation is followed by thorough rinsing and soaping to remove the unfixed proportion of dye. Stronger alkalis, such as sodium hydroxide and trisodium phosphate, can of course be used but, as they increase the reactivity with the fiber, there is a greater danger of hydrolysis for the proportion of dye not reacted with the substrate.

In comparison with the next comparable dye of French Pat. 1,330,585 and British Pat. 1,022,043 the dyes produced in accordance with the present invention exhibit a higher degree of reactivity.

In the following Examples the parts and percentages are by weight and the temperatures are expressed in degrees centigrade.

Example 1 85.8 Parts of the copper complex compound of l-(2' -hydroxy-4-sulpho-6'-aminonaphthyl)-5-(2"-hydroxy- 5"-sulphophenyl)-3-for:mazyl-carboxylic acid-(6"'- sulphonaphthyl-l"'-amide) in the form of the trisodium salt are dissolved in 550 parts of water. The solution is adjusted to pH 5.0 with 30 percent acetic acid and clarified by filtration, on which it is run into a reaction vessel fitted with a reflux condenser. 32 Parts of crystallized sodium acetate are added, followed by sodium carbonate to bring the pH to 6.0. Eighteen Parts of 2,4,6-trifluoro-5-chloropyrimidine are added within 2 hours at l020 with stirring and with the controlled addition of dilute sodium carbonate solution to maintain the pH value in the range of 6.0 to 6.5. Subsequently stirring is continued at l020 until no further free amino groups are indicated. The reactive dye formed is then salted out with sodium chloride, filtered off, washed with aqueous sodium chloride solution and carefully dried with vacuum. On grinding it is obtained as a dark powder which dissolves in water to give green-blue solutions. This new dye is the copper complex of the formazane of the formula or, more exactly, a tautomeric form of this formazane. The aminoformazane dye employed in this reaction can be prepared by coupling diazotized l-amino-2-hydroxy-6-nitronaphthalene-4-sulphonic acid with the hydrazone of glyoxylic acid-(6-sulpho)-naphthylamide and 2-hydroxy-l-hydrazinobenzene-S-sulphonic acid in the presence of a copper-yielding agent to yield the copper complex compound of l-(2'-hydroxy-4'- sulp ho-6'-nitronaphthyl)-5-(2-hydroxy-5"- sulphophenyl)-3-formazylcarboxylic acid-6"- sulphonaphthyl-l "-amide) in the form of the trisodium salt. 88.8 Parts of this salt are dissolved in 500 parts of water at 65, 17 parts of anhydrous sodium sulphide are added and the solution is stirred at 65 until reduction is complete. The aminoformazane dye can be salted out and isolated, or alternatively employed in the dissolved form.

Example of Application in Pad Dyeing A mercerized, bleached cotton fabric is padded with a liquor containing 2 percent of the dye of Example 1, 1 percent sodium sulphate and 0.3 percent sodium carbonate, expressed to retain 70 percent of its weight of the liquid, rolled up and the roll lapped in plastic sheet to exclude air and so prevent partial drying at the edges. The dye solution and the solution of sodium carbonate and sodium sulphate are prepared separately and blended immediately before padding, preferably by means of an automatic mixing device. The roll of fabric is stored for 6 hours at 20-3 and afterwards is rinsed with cold and hot water, soaped for 20 minutes at the boil with a solution of 2 parts of a non-ionic detergent in 1,000 parts of water, rinsed again and dried. A green-blue dyeing is obtained which is fast to washing and water.

The nickel-containing reactive formazane dye produced in an analogous manner, on application to cotton fabric by padding, gives a dyeing of comparable fastness but with a slightly less greenish shade.

Example of Application in Printing A cotton sateen fabric is printed with a paste prepared with 40 parts of the dye of Example 1 100 parts of urea 380 parts of water 450 parts of 4 percent sodium alginate thickening parts of sodium l-nitrobenzene-3-sulphonate parts of anhydrous sodium carbonate 1,000 parts Example of Application in Exhaustion Dyeing Two parts of the dye of Example 1 are dissolved in 4,000 parts of cold water and the solution raised to on which two parts of 100 percent acetic acid and three parts of a mixture of a polyoxethylated fatty amine and an alkylpolyglycolether are added. into this dyebath are entered 100 parts of a wool fabric. The bath is brought to the boil in 10-20 minutes and held at the boil for -60 minutes. Subsequently about three parts of 25 percent ammonia and three parts of hexamethylenetetramine tetramine are added at -90 and treatment is continued for 20 minutes at The dyed fabric is rinsed thoroughly, with some acetic acid added to one change of rinsing water, and dried. A level green-blue dyeing is obtained which is fast to washing, perspiration, water and milling.

In the following table further metal complexes of formazane dyes conforming to the present invention are specified. In the metal-free form they have the general formula and in the table they are distinguished by the significance of the symbols Y and X, by the metal used for complex formation fastness to light and wet treatments. 35 and by the shade of the dyeing on cotton.

W 7 7' I I TABLE OH OH Ex. I Shade on No. A B Y X Metal cotton 2 OH OH CON(C:H5)2 Cl Cu Navy-blue.

I l S 03H S 03H Cu Do. (1 011 D0.

5 OH do Cl Cu D0.

- -C ONE- OzN l S 03H 6 Same as above do Same as above F Cu Do. 7.- "do d0 "do CH; CH D0.

8. (I)H d0 -CONH(CH )3OCH1 C1 C11 D0.

i CH3 9 0H do C H Cl Ni Grey-violet.

Cl CONHCHzCH-C4H9 SOaH TABLE-Contiuued 01-1 0H Ex. I I Shade On No. A B Y X Metal cotton 10 '.'d'5'.'; II. .I. A EBJH 01 Cu Grey- H03s- CONH- -OH 11 OH OH -coNHcH,cH,oH 01 Cu -w p,

HOaS- @s0m I l SOaH 12 ameasabove Same asabove Sameasabove H C11 D0- 13. 0H H 01 Cu Do.

I c0NH- H SOaH SO|H 14 O H O H G1 On Navy-blue.

v CONHCH --C HOaS- I i c1 SOBH 0H 0H CONHC5H11(I1) 01 on HOaS-O 16 OH OH 7 T51 11 01 Cu D0.

HOOC O OSO3H -0 ON-C l SO H 17 0H OH /j 01 Cu D0.

CO-N H 0 HOaS- I l SOaH $03K 18 0H Sameasabove CON(C2H4OH) .4 01 Cu Do- I som 19 'OH 50 11 H 011 'D TABLE-Continued OH OH Ex. I I Shade on No. A B Y X Metal cotton 20 OH 0H 01 Cu Grey-blue.

CONH-OS 0mm HOa'S- I I S 0 H 01 21 ()H OH OGH3 v C1 Cu D0 HO3S- SO H -CONH-C I I Cl 2 (|)H Same as above C1 C1 Cu Grey-violet.

I CONHQSO3H I S OgNHCHg 23 (|)H 11 s 0 H C1 Cu Blue.

I c1 CONH 24 0H CH C1 Cu B1ue.violet.

I I I -OONH O O -s 0111 I I S 5H 2 z b)2 25 Same as above Same as above Same as above F Cu D0 26. 11 OH 15 0 H G1 On Do 0 I O [I) I I S OaH S 03H 27 (')H ([311 S|O H 01 Cu DO.

O O C ONE-8 I I I S OzNH- NO; S 0 H 28 OH OH Br Cu Navy-blue.

I I CONH I I S 03H S 03H Same as above Same as above Same as above CI Cu D 30.4... 011 do V w Cl Cu 170- TABLE-Continued OH OH Ex. I I Shade on No. A B Y X Metal cotton 31 OH OH CI Cu Green.

I 0 ON H HO: 5-8 s 03H 32 OH OIH C1 Cu N avy-blue.

HO; S S 03H I I S 0 H S 0 H as 0H Same as above 0x Cu Grey-blue.

O ONH- I al 34 OH OH 01 Cu Olive-grey.

C ONH- S OaH S OaH I H: N 2

35 CIJH ()H I 01 Cu Navy blue.

0 O NH CHaC 0-HN Cl I I S 0 H S OaH as ([)H ?H ?O H 01 Cu Grey-violet.

- C O-NI-I- I I S OzNHs S OzNHz S 0 H I 37 (In! (|)H H C1 Cu Navy-blue.

H O3SU U I I C H; S 0 1! 38 (I) II Same as above. II F Ni Violet-brown.

I S 0 H 39.. Same as above. do II C1 C11 Navy-blue.

40 (III (|)1[ --CONHC4Hq CI Cu DO- I IIO3S- -S 0.1"

TAB'LE c'ontmueii OH OH E I I Shade on No A B Y X Metal cotton 41. OH OH II CI Cu Grey-blue.

O-s 03H 42 OH 011 CI Cu Navy-b11112 IIOuS- I S 03H S 03H 43 OH OH I C! Cu Grey-blue CONH- Y S 0 H I s 03H CgH5O 44 OH OH O O-NH Cl Ni Grey-violet.

l I I Br S 0 H S O:NH2 45 on 11 c O-NCHg-CH=CH2 01 Cu Navy-blue- }IO3S S 0 H CH3-?CH3 46 Same as above 0H CONHC1ICOOII 01 Cu Do (1H CI'I(CH3)2 I S OaH 47 d0 Same as above -CONI-IC I ?H 0] Cu Do.

N O I l HN 48 "do d0 -CONII-CH -CII 7 CI Cu D0- NH N I 49 .do ..d0 -CONHCH; I C1 Cu D0.

50 .d0 do C ONHCH 01 Cu D0- 51 "do do x. -GONCH;CH OH C1 C11 D0.

TABLE-Continued OII OH Ex. I I Shade on No. A B Y X Metal cotton 52 10 .410 CONH (CH;) 01 Cu Do.

O-ClI(CHa)2 53 do do --CONHC(CH3)3 01 Cu D0- 54 do .Q. .do -COI?TH I 01 Cu Do.

I a)a 55 db -.clo Cl Cu Do.

-CON-CH; JH1COCH 56 do do 01 Cu Do.

CON

57 ..do do 01 Cu D0. CON

ss--' OH OH 01 cu Blue-violet.

| CO1 II- I CH S 03H l 1 I S 03H S 07-CH(CH5)2 69 Same as above OH H 01 Cu Navy-blue.

- CON C1 NHGO I CH3 0 I (EH5 SOJH 60 -do CH C O NHCH -([3 H1 C1 C11 Blue-violet.

| SOrNII I SOaH 61 OH OH CONHCH 0! Cu Navy-blue.

Same as above -CONHC H Cu Do. do.. CON(CH3) Cu Do. -do- -CONHCH;C Cu Do. do CONHCHCHCH3 01 Cu D0.

66 d0 do -CON(CH;CHCH3) C1 C11 67 ..d0 (1o CONCH CH;OH Cl Cu 0- 68 .-d0 .do -CONHCH COOH C1 C11 69 d0 ,d0 CONOH COOH C1 C11 0- TABLE-Continued OH OH Ex. I I Shade on No. A B Y X Metal cotton 70 OH -do CON(C H 11) 01 Cu D0.

HOzS

I S 01H 71 Same as above do 01 C 1 D -CONH 72 ..d0 do 01 Cu Do.

0 ON-- OCzHs JH:

73 -.d0 .do 01 Cu D -C ONH- H CH:

74 "do .do 01 Cu 1m 0 OI-II H E HO-CHCH3 75 ..do .do Cl Cu Do.

-0 ON-CH2C|3H 01 Cu Do. C 01? H E CH2COOH 01 Cu Do. C ONH- H OH CONHCmHz| Cl Cu D0. CONHCH(CH2)10CH2 Cl Cu D0.

80 ..do do CI Cu D0.

CONH(CHz)4 H 81 do n do -CONHCH(CH )5CH, Cl Cu Do.

82 ..do do --CONHC!3HCOOII Cl Cu D0.

(CHzhCOOH 83 do do COI@COOH 01 Cu Do.

84 ..do ..d0

CON H CaH-l Cl Cu D0.

85 -do do (3H C! On D0 86 do d0 Cl Cu Do.

CONH Br 87 d0 do Cl Cu D0.

-CONHC CH3 88 V "(1Q d 01 Cu DO- -c O-NH-Q 89 "d do G 01 Cu Do.

TABLE-Contlnued OH OH Ex. I Shade on No A B Y X Metal cotton 90".. OH H CH; 01 Cu Do.

HOaS O O--NH- CH:

| S 0311 S 03H 91... Same as above Same as above. CH; 01 Cu D0.

0 ONH- 92 "d0 (|)H C ONH-CzH4- S 03H C1 011' D0- HOa S- 93 -.do Same as above (I311; Cl Cu D0- --C O--N-CZH4 S 03H formulas of representative dyes of the foregoing Exam- Example 18 ples are as follows:

The copper complex compound of.the formula Example 8 The copper complex compound of the.formula I SO II SOaIl F The copper complex compound of the formula The copper complex compound of the formula on n! N Hols N=NCH=NNH --NH 17F 01 \OgH SOaH Example 42 The copper complex compound of the formula We Claim. 3. The complex, accordingto claim 1, of copper and v 1. A complex of copper and a compound of the fora compound of formula mula H N OH OH N=N(l3=N-NH NH T4 60 O-N N NH /N F l N I i gwmnoom I I =0 soan soan 1 Ill 01 808E SO'H l 4. The complex according to claim 1, of copper and a compound offormula I OH OH A wherein l l N N= C=NNH NH T11 01 /N- N(C:H|OH):| I R: SO|H 03H F 5. The complex according to claim 1, of copper and a is N,N-diethylamino, N-S-methoxypropylamino, compmmd f formula N,N-di-(2-hydroxyethyl)amino or N-phenylamino.

OH 7 7 "OH 2. The complex, according to claim 1, of copper and a compound of formula Hogs NH W 7 WM 01 L 011" OH 0 I N S0111 01K F -N=NC[=N-NH NH T4 I 01 N NH N(C:H5)2 X SOQH 302E F UNITED STATES PATENT OFFICE QERTIFICATE OF CORRECTION- Patent No. 3'. 725 382 Dated Anril 3 1973 Inventm-(S) Philippe Grandjean It is certified that error appears in the above-identified patent m: said Letters Patent are hereby corrected as shown below:

Column 2 line 16,

add SO2NHC2H4OIH after I CH3 I I Column 2 line 19 I I h I I I I I I delete IS0 NHC H och Column 2 line 37 l I I I I delete "alkylene" and insert therefor ---alkehyl---'.

Column 2 line 63 delete 3 n R and insert therefor 3 -CO- v o I I 4 v FORM "$69) I uscoMM-oc scan-Pea UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3.725,382 Dated April 3, 1973 inventofls) Philippe Grandjean PAGE 2 "it is certifiedvthat error appears in the above-identified patent and .a; said Letters Patent are hereby corrected as shown below:

Column 2 line 67,

delete R CON R and insert therefor Column 3 line 7,

delete the after lhydroxybutyl-2 and insert therefor and I C I Column 3 line 9 delete the after hydroxyethyl)- and insert therefor -and-. I

Column 4 line 10,

delete "30 and insert therefore -20 lumn 5 line 1,

delete "food'? and insert therefor -good-.

FQBM 0 9- I usco -Dc wan-P99 fi u.s. sovzmmsm rnmmqa 01:"?! I!!! o-eu-au 1 UNITED STATES PATENT OFFICE @ERTIFICATE OF CORRECTION Pate-m: NO. 3,725,382 Dated April 3, 1973 7 PAGE 3,"

Iriventor(S) Philippe Grand-lean it: is certified that error appears in the above-identified patent ls-11L said Letters Patent are hereby corrected as shown below:

Column 7 line -2 delete "liquid" and insert'therefor --1iquor.

Column 8 line 12 delete the word "tetram ine".

Column 7-8 example 8, Y A column,

delete and insert therefor so H FORM po-zvso (10-63) uscoM -pg: cda'ro-pqq w u.s. sovznumzur rpm-rm; orflgg': pig 0 360-3341.

33 a Dated p il 3, 1913 Patent No. 13

Inventor(s) PhilippeGfrandjean PAGE 4 g, 1 It: is-certified that? error appears in the above-identified patent and that seidLetgslPatEent are hereby corrected as shown below:

Column 9-10, B column,

'delete and insert fihrefo: OH

UNITED STATES PATENT OFFICE- CERTIFICATEOF CORRECTION- Patent No. 3725382" Dated April 1973 G lnventm-(s) Phlllppe Grand ean A L 5 It is certified that error appears in the above-identified patent that said Letters Patent are hereby corrected as shown below:

0H Column 9-10, example 13, B column,

delete and insert UNITED STATES PATENT OFFICER CERTIFICATE OF CORRECTION Patent 3,725,382 Dated April 3; 1973 Inventor(s) Philippe Grandjea'n PAGE 6 "it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

. OH Column 11-12, example 24, B column,

delete II II z z s 2 and insert therefor SOZN (CZHS) 2 7 Column 11, example 27, shade on cotton (column;

delete "Do." and insert therefor --greyblLie'-. Column 22, line 41 delete "37" andinsert therefor --39--.

F or-m 0 1050 (10-69) UsCOMM-Dq 608 76-P69 1: us. eovznnnzn-r PRINTING orrlc; jg 0-in-3.

UNITED STATES PATENT OFFICE e QERTIFICATE OF CORRECTION Patent No- 3,725; 382 v Q Dated April 3, 1973 d 4'- Inventor(s) 'p'h- 1 Grandj ean IIAQL 7 It is certified that error appears in the shove-identified patent end the": said Letters Patent are hereby corrected as shown below:

Column '23, line 14, claim 1,

- insert I or the compound of the formula OH I I 7 H I I, I. i (If WWI:

Column 23, line 22,

delete the after."methoxypropylamin fi and insert I therefbi -o r- I i Column 23, line. 23,

delete "er tI-phehylaminp" Column 23, line 25 insert the word -'theafter '...a compound of FORM P0 1051, (10-69) I 2 USCOMM-DC scan-Poo I #1 U. S. GOVFRNMENT PRINTING OFFKE "I, O-{il-lll.

Claims (4)

1. 2. The complex, according to claim 1, of copper and a compound of formula
2. 3. The complex, according to claim 1, of copper and a compound of formula
3. 4. The complex according to claim 1, of copper and a compound of formula
4. 5. The complex according to claim 1, of copper and a compound of formula